JPH04272911A - Curable fluorinated copolymer, preparation of the same and its application to paint and varnish - Google Patents

Abstract

Curable fluoro copolymer containing the residues from copolymerisation of a fluoro monomer and of an allyl monomer, characterised in that   a) the residues of fluoro monomer originating from the combined use of tetrafluoroethylene and of at least one other fluoro monomer chosen from chlorotrifluoroethylene and vinylidene fluoride   b) the allyl monomer is an allyl polyol of formula <IMAGE>   R1 being H or CH2OH   R2 being OH or CH2OH   R3 being CH3 or OH <??>it being known that R1 and R3 cannot simultaneously be H and CH3 and in that it contains:   c) the residues of an allyl or acrylic monomer bearing a fluorocarbon chain of formula <IMAGE> with   n being a value from 3 to 12   R4 being H or CH3   X being <IMAGE> <??>This curable copolymer is obtained by copolymerisation in solution in an organic solvent. In solution in a suitable solvent, this copolymer is employed in paints or varnishes which resist stains and dirt.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to the use of tetrafluoroethylene (C2F4) and chlorotrifluoroethylene (C2F4).
C2 F3 Cl ) and vinylidene fluoride (
at least one selected from C2 H2 F2 )
The present invention relates to curable copolymers constituted by other types of fluorinated monomers, allyl polyols, and allyl or acrylic monomers having fluorinated carbon chains. The copolymers of the invention are soluble in organic solvents and are particularly suitable for the production of paints and varnishes whose primary objective is stain and stain resistance. [0002] Fluorinated copolymers have excellent mechanical properties,
Although it is known to have chemical and weather resistance, its lack of solubility in common solvents makes it difficult to use in certain applications, such as paints and varnishes (in these areas, it has high resistance). However, it cannot be used as a resin for fluorinated copolymers, in which the properties of fluorinated copolymers are desired in order to produce coating materials that are easy to handle. In order to eliminate the above drawbacks and take advantage of the properties of fluorinated polymers, attempts have been made to solubilize fluorinated polymers in common solvents. It is known to copolymerize an at least partially fluorinated unsaturated ethylenically monomer with a fluorinated polymer to reduce crystallinity. Due to their low crystallinity, the copolymers generally have poor mechanical properties, especially low hardness. Therefore, when used in applications such as paints and varnishes, it is desirable to incorporate functional groups into the structure to make it curable and maintain sufficient rigidity. Such curable fluorinated copolymers are disclosed in French Patent No. 2488260.
listed in the number. This copolymer has a fluorine atom at the α-position carbon in the main chain. This is an essential condition for producing a product with excellent aging resistance. Also, α of the main chain
When a fluorine atom exists in the carbon position, dust becomes difficult to adhere to.
This results in fluorinated paints having a slower fouling rate than other paints. However, even if a fluorine atom is present at the α-position carbon in the main chain, graffiti resistance cannot be completely satisfied for light-colored paints. In other words, graffiti leaves traces (ghost images) even after it is erased. In order to improve the stain resistance, the solutions described in the following patents have been mainly investigated: European Patent No. 186186 discloses that in order to prevent the paint film from being rapidly contaminated by dust, A fluorinated polymer having an active site and: CF3-(CF2)n-CH2-CH2
-OH or OH-CH2 -CH
A stain-resistant paint is described which is characterized in that it is combined with a specific fluorocarbon compound of 2-(CF2)m-CH2-CH2-OH. However, even when these compounds are added in small amounts, they generally do not improve stain resistance, and when used in large amounts, they limit the crosslinking of the paint film, causing the negative effect of causing pigments in paints and varnishes to stand out, resulting in uneven coloring. There is. European Patent No. 311,052 describes stain-resistant paints obtained by combining fluorinated polymers with special copolymers containing fluorine in the form of polyfluorocarbon chains and containing hydrophilic monomers. However, the inclusion of this special copolymer is not preferred from the viewpoint of aging resistance of the paint. Current stain resistance to soiling and repeated cleaning is not permanent and remains an open problem. SUMMARY OF THE INVENTION It is an object of the present invention to provide a solution to this problem. In addition to the above-mentioned properties, the fluorinated copolymer of the present invention can be easily cured in the presence of a curing agent. Films with excellent adhesion can be formed on substrates such as ceramics, wood, plastic materials or previously applied coatings. Means for Solving the Problems The present invention provides a curable fluorinated copolymer comprising a copolymerized residue of a fluoride monomer and an allyl monomer, comprising: (a) a copolymerization of the above-mentioned fluoride monomer; (b) the copolymerized residue of the allyl monomer is derived from a combination of tetrafluoroethylene and at least one fluoride monomer selected from chlorotrifluoroethylene and vinylidene fluoride; The following [Chemical 7]: [Chemical 7] (Here, R1 is H or CH2OH, and R2
is OH or CH2OH and R3 is CH3
or OH, and R1 and R3 cannot be H and CH3 at the same time), and furthermore, (c
) The following [Chemical formula 8]: [Chemical formula 8] (where n is 3 to 12, and R4 is H or CH
3, and X is CH2-O or the following [Chemical formula 9]: [0
[008] It is characterized by containing a residue of an allyl monomer or an acrylic monomer having a fluorinated carbon chain represented by the formula: The copolymer of the present invention has CH2=CH-O
-R5 (wherein R5 is a linear or side-chain alkyl group having 2 to 13 carbon atoms) optionally further comprising a non-hydroxylated vinyl ether residue; Can be done. [0010] The curable copolymer of the present invention generally has the following composition per 100 moles of total copolymerized monomers: Tetrafluoroethylene: 14 to 45 moles;
Chlorotrifluoroethylene, vinylidene fluoride or a mixture thereof: 25 to 81 mol, Allyl polyol: 4 to 15
mol, fluorocarbonated allyl monomer or acrylic monomer: 1 to 17 mol. The solubility of this copolymer in common solvents for paints and varnishes is greater than that of the fluoride monomer components C2 F4 , C2 H2 F2 , C2 F3Cl
can be adjusted by selecting an appropriate value. Generally, it is preferable to employ the following two types of monomer components: The first component is a component containing a large amount of vinylidene fluoride, and the ratio of the number of moles of C2 H2 F2 to the total number of moles of C2 F4 and C2 F3Cl is is below [Formula 3]
: [Formula 3]. The second component is C2 H2
A component with a F2 content of 20 mol or less, C2 F
It is characterized in that the ratio of the number of moles of C2F3Cl to the number of moles of C2F3Cl is as follows [Formula 4]: [Formula 4]. Preferred allyl polyols include 3-allyloxyl-1,2-propanediol and trimethylolpropane monoallyl ether. Preferred allyl monomers and acrylic monomers having a fluorocarbon chain include the following [
Compounds represented by the formulas [Chemical formula 10] to [Chemical formula 14] can be mentioned. [Formula 10] [Formula 11] [Formula 11] [Formula 12] [Formula 13] [Formula 13] [Formula 14] [Formula 14] When vinyl ether is incorporated into the copolymer composition, , butyl vinyl ether, isobutyl vinyl ether, prolyl vinyl ether and isopropyl vinyl ether. In order to use the copolymers of the present invention in the composition of liquid coatings such as paints and varnishes, it is necessary that the intrinsic viscosity of a solution of the copolymers at a concentration of 1 g/dl in dimethylformamide solution at 25°C is 0. It is preferable that it is 0.06 to 1 dl/g. The presence of C2F4 is essential if the allyl polyol is incorporated into the copolymer chain. If this amount is lower than the above 14 mol%, the productivity will be low, especially the polymerization rate will be low, and if this amount is higher than the above 45%, the obtained copolymer will not be sufficiently contained in the paint solvent. The problem arises that it does not dissolve. In order to increase the solubility of the copolymer in common solvents, it is preferable to add a non-hydroxylated vinyl ether during copolymerization. Total base monomers necessarily added to the composition of the curable copolymer of the present invention 10
The addition of up to 33 moles of unhydroxylated vinyl ether per 0 mole does not have any adverse effect on the final copolymer. The copolymer of the present invention can be produced by a known conventional solution polymerization method. In this solution polymerization method, polymerization is performed in a solvent at a temperature of about 30°C in the presence of an initiator soluble in an organic solvent.
~120℃, preferably 40~80℃, pressure about 10~
The respective monomers are copolymerized at 80 bar, preferably from 15 to 40 bar. The crosslinkable copolymer of the invention comprises tetrafluoroethylene and at least one other fluorinated monomer selected from chlorotrifluoroethylene and vinylidene fluoride and a fluorocarbon as defined above. It is obtained by copolymerizing an allyl polyol having a chain with an allyl monomer or an acrylic monomer. Each component is used in the following amounts per 100 moles of copolymerized monomer: Tetrafluoroethylene
14-45 mol Chlorotrifluoroethylene, vinylidene fluoride or mixtures thereof: 13-81 mol Allyl monomer in allyl polyol form: 4-1
Allyl or acrylic monomer with 5 molar fluorocarbon chains: 1 to 7 mol. It is also possible to add the unhydroxylated vinyl ethers defined above in proportions of up to 33 mol per 100 mol of these monomers. In a preferred polymerization method of the present invention, a previously degassed solvent is heated in a reaction tank to a predetermined reaction temperature, and then
C2 F4 and C2 F3Cl and/or C2
Mixtures with H2F2, as well as other monomers,
If necessary, a mixture containing a starting component of non-hydroxylated vinyl ether is also introduced into the reaction vessel. The amount of monomer mixture introduced to achieve a given reaction pressure depends on the amount of C2F4 in the chosen solvent,
It depends on the state of dissolution of C2F3Cl and/or C2H2F2. C2 F4, C2 F3C
The weight ratio of the mixture of 1 and/or C2 H2 F2 to the solvent is usually from 0.1 to 1. When the reaction pressure and temperature reach predetermined values, a polymerization initiator is added. As the polymer is formed the pressure decreases so C2 F4,
A mixture of C2F3Cl and/or C2H2F2 is added to compensate the pressure. In this case, C2 F4 and C2 F3 with the same molar composition as those added initially
A mixture of Cl and/or C2 H2 F2 can be added. Furthermore, in order to produce a copolymer with a uniform composition, the composition of the mixture introduced during the polymerization process can be adjusted by taking into consideration the reactivity specific to each monomer. Other monomers and optionally non-hydroxylated vinyl ethers can be added during the polymerization. These can be added as a mixture or individually and also in combination with C2F4, C2F3Cl and/or C2H2F2. These other monomers and the optional non-hydroxylated vinyl ether are preferably added such that the composition of the mixture of all monomers remains constant throughout the copolymerization process. C2F4 and C2F3Cl added to maintain reaction pressure
The mixture with C2 H2 F2 and/or C2 H2 F2 is preferably added continuously for a sufficient period of time until the dry extract reaches a concentration of about 10 to 60%, preferably about 15 to 40%. Volatile residual components can be removed by degassing. The solution removed from the polymerization reactor can be stored as is if the polymerization solvent is suitable for use in paints and varnishes. If this is not the case, the solvent can be removed by distillation and replaced with another solvent more suitable for the desired application. Also, wash the solution with water and
It is also possible to remove water-soluble residues produced during the copolymerization process that adversely affect storage stability. The solvent used in the copolymerization reaction must dissolve the monomer mixture and must be inert to other reaction components. Preferably, this solvent is selected from acetates and alcohols. Among the preferred acetates, mention may especially be made of butyl acetate, isobutyl acetate and ethyl acetate. Preferred alcohols include n-propanol and tert-butanol. The copolymerization initiator itself is known, and is generally a radical polymerization initiator, such as purge carbonate,
Perpivalate and azo compounds, such as diisopropyl or dicyclohexyl percarbonate, tert-butyl or tert-amyl perpivalate, azobisisobutronitrile and azobis-2,2-
Preference is given to choosing among dimethylvaleronitrile. The number average molecular weight (Mn) of the resulting crosslinkable copolymer is preferably from 1,000 to 20,000. This value is determined at room temperature by sterically hindered chromatography (GPC/gel permeation chromatography) after dissolving in dimethylformamide. This GPC measurement was performed using a WATERS 3-column microstyla gel device (102 nm, 103 nm,
104 nm) and calibrated with polyethylene glycol standards. Detection is performed using a refractometer. [0029] In a solvent, the copolymer becomes a transparent solution. Add to this solution the desired coating additives, such as pigments, fillers, solvents, diluents, catalysts, flow modifiers, spreading agents, wetting agents, antifoaming agents, heat and light stabilizers, fixing agents, etc. A resin (coresin) or a crosslinking hardening agent can be added. As pigments, mention may be made of titanium oxide, iron oxide, chromium oxide green, cobalt blue, chrome yellow, carbon black or anti-corrosion pigments such as zinc phosphate or aluminum triphosphate. As solvents and diluents, mention may be made of esters, ketones, propylene glycol ethers and aromatic compounds. Coresins include acrylic resins, polyesters, polyethers and epoxides. As the crosslinking curing agent, mention may be made of optionally etherified melamine formaldehyde, free or blocked isocyanates or polyisocyanates, and organic acids or organic polyacids or their anhydrides. The crosslinking temperature of the copolymer of the present invention is usually -20 to +270.
°C, which basically changes depending on the type of curing agent. The crosslinking ability of the fluorinated functional copolymer is determined by a solvent resistance test. Soak a cotton pad in methyl ethyl ketone (MEK) and rub the paint film back and forth until the base is visible. In this case, a total of 50 or more back and forth movements indicates good crosslinking, and a value of 100 or more indicates very good crosslinking. Paints and varnishes based on the copolymers of the invention can be applied using an air gun, electrostatic spray, dipping or with a brush or roller. Examples of the present invention will be shown below, but these are not intended to limit the invention. EXAMPLES In the following examples, stain resistance capacity was measured in several different ways. The first method is ZISM
AN) method is used to measure the critical surface tension of a coating film. In this method, the contact angle θ is measured using a series of liquids whose surface tensions τL are successively decreased, and the critical surface tension τC
Determine. Calculate cos θ as a function of τl and obtain the maximum value of τl that indicates complete wetting of the paint (θ=0) with cos θ=1. This value corresponds to the critical surface tension τC of the coating film, and the smaller the value of τC, the higher the stain resistance. The above series of liquids are as follows: (1) Fresh double distilled water (within 24 hours)
(2) double distilled glycerol, (3) diiodomethane, and (4) benzyl alcohol. Contact angles are measured using a RAME-HART type goniometer. [0032] The second method is to evaluate stain resistance against standard staining agents. At least 4 coated substrate surface
Contaminate a cm2 circular area with the following standard staining agent:
(1) Product name: KIWI black shoe cream (2)
Black indelible felt-tip pen with product name PENTEL (3) Fluorescent pink graffiti paint with product name ALTONA. After one week of infiltration, the standard staining agent is removed using a cotton pad soaked with methyl ethyl ketone. Change the cotton pad as often as necessary to allow the solvent-soaked cotton pad to absorb dirt. This removal operation is considered complete when no trace of dirt is visible on the pad after rubbing with the cotton pad by moving it back and forth five times. Traces or traces of residual product are evaluated visually or using a spectrophotometer as a difference in chromaticity from an untreated standard. When testing visually, the degree of remaining contamination is evaluated in the following way: 0 = No trace 1 = Colored trace observed from 25 cm 2 =
Colored traces are not observed from a distance of 30 cm or more. 3 = Colored traces are not observed from a distance of 2 m or more. 4 = Colored traces are not observed from a distance of 5 m or more. The durability of stain resistance is measured by staining a 4 cm 2 circular area on the surface of a painted test piece. The contaminated specimen is left at room temperature for 3 minutes, baked at 100°C for 3 minutes, and then cooled to room temperature. Next, wipe with a cotton pad moistened with methyl ethyl ketone (MEK). To ensure that the cotton pads can absorb dirt, replace as many cotton pads as necessary. The cleaning operation is considered complete when the clean cotton pad is rubbed back and forth five times and no trace of dirt is visible on the cotton pad itself to the naked eye. The remaining traces are evaluated by the naked eye or using a spectrophotometer as a difference in chromaticity from the untreated standard product according to the above criteria. Example 1 (comparative example) In a 3.3 liter autoclave equipped with an effective stirring device, 2 liters of tert-butanol and 30
g of 3-allyloxyl-1,2-propanediol and 10 g of formula: C8 F17C2 H4 -O-CH2
A fluorinated monomer represented by -CH=CH2 is introduced. The temperature of the autoclave was set to 70℃, and at this temperature 215g of C2 H2 F2 and 84g of C2
After adding F4 and 84g of C2 F4, 5g
of tert-butyl perpivalate. The pressure is 2
0 bar. When copolymerization occurs, the pressure decreases, so the molar ratio of C2 H2 F2 and C2 F2 is 65/35.
4 to compensate the pressure. For every 46 g of the monomer mixture defined above, 5.5 g of 3-allyloxy-1,2-propanediol and 1.8 g of the formula: C8 F17C2 H4 -O-CH2 -CH=
Add a compound of CH2. After polymerizing for 3 hours,
8 g of tertiary butyl perpivalate are introduced to increase the rate of copolymerization. After 6 hours and 10 minutes, a total of 44 g of 3-allyloxy-1,2-propanediol and 14
g monomer C8 F17C2 H4 -O-CH2-
CH=CH2 and C2H with a molar ratio of 65/35
414 g of a 2F2/C2F4 monomer mixture were introduced. The autoclave is cooled, residual monomer is degassed, and the contents of the autoclave are distilled under reduced pressure. 445
g of the copolymer is recovered and dissolved in butyl acetate. The dry extract of the copolymer solution after washing with water is 6
It is 4.4%. The hydroxyl groups of this copolymer in a pyridine/phthalic anhydride solvent were chemically quantified. This solvent is prepared by dissolving 140 g of phthalic anhydride in 1 liter of pyridine in a glass flask. 1 g of copolymer is placed in 5 ml of reagent and maintained at 95-100° C. for 1 hour. After cooling, the consumed phthalic anhydride is determined. As a result of the measurement,
1.70 meq/g of OH was determined. Fluorine 19
As a result of NMR analysis, the molar composition of the copolymer is as follows [Chemical formula 1
5] was confirmed. Concentration 1 g in dimethylformamide solution at 25°C
/dl, the intrinsic viscosity of the copolymer was 0.19 dl/g. Test 1 100 g of the above copolymer solution, 12.5 g of isophorone diisocyanate, and 2.3 g of a 10% butyl acetate solution of dibutyltin dilaurate (DBTL) are mixed. The viscosity is adjusted using 12.5 g of methoxylpropanol acetate. 1 of the obtained varnish
0.7 mm thick using a 00 μm spiral applicator
applied to a deoiled, chromium-treated aluminum plate. The test piece was left to dry at room temperature for 48 hours, and the thickness was 30μ.
m dry coatings are obtained. This coating did not change even after rubbing with methyl ethyl ketone 100 times in a back and forth motion. This coating exhibited a Persoz hardness of 220s when measured according to NFT30016, and a specular gloss at 60° of 60% when measured according to ASTM standard D523-85. The critical surface tension was 34 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Test 2 120 g of titanium dioxide, 160 g of the above copolymer solution, and 40 g of butyl acetate were rotated at 1500 rpm.
Prepare the base by dispersing for 30 minutes. Add 20g of the above copolymer solution to 160g of this white base, and 21.5g
a hexamethylene diisocyanate trimmer; 2.
6 g of DBTL in 10% butyl acetate solution and 10
g of butyl acetate. 1 of the obtained paint
0.7 mm thick using a 00 μm spiral applicator
Apply to a deoiled, chromium-treated aluminum plate. The specimen was left at room temperature for 48 hours to dry to a thickness of 28
A dry coating of μm is obtained. This coating film did not change even after being rubbed 100 times with MEK in a back and forth motion. This coating film has a Persauz hardness of 2 when measured according to NFT30016.
The specular gloss at 60° measured according to ASTM standard D523-85 was 43%. The critical surface tension was 37 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Test 3 The same paint as in Test 2 was prepared, and the coated board was heated at 80°C for 30 minutes.
Bake for a minute to dry. The 28 μm thick dry paint film did not change after 100 rubs with methyl ethyl ketone in a back and forth motion. This coating is NFT 30016
It showed a Persauz hardness of 228s when measured by ASTM
The specular gloss at 60° measured according to standard D523-85 was 46%. Critical surface tension is 37.7mN/
It was m. The results of the stain resistance test and its persistence test are shown in the attached table. Example 2 (Comparative Example) Test 4 Commercially available fluorinated copolymer (molecular weight 20,000, OH index 32 (
Copolymer of chlorotrifluoroethylene and vinyl ether) having a transition temperature of 422±2° C. in a 60% xylene solution. A pigment base is prepared by dispersing 118 g of titanium dioxide in 196.5 g of this commercially available copolymer at 15,000 rpm for 30 minutes. Next, 78.6 g of the base material was prepared using 21.7 g of the commercially available fluorinated copolymer.
dilute. Add 7.95 g of heximethylene diisocyanate trimer and 0.2 g of DBTL in 10% butyl acetate. The viscosity is adjusted using 19.8 g of butyl acetate. The obtained paint is 100μm
It was applied to a deoiled, chromium-treated aluminum plate with a thickness of 0.7 mm using a spiral applicator. The specimens are left to dry at room temperature for 48 hours to obtain a dry coating with a thickness of 26 μm. This coating film is made of MEK with a back and forth motion.
It does not change even after being rubbed several times, and has a persaud hardness of 237s when measured according to NFT30016, and has an ASTM standard D.
Specular gloss at 60 degrees measured according to 523-85 is 7
It was 8%. The critical surface tension was 39.5 mN/m. The results of the stain resistance test and its persistence test show that there are limitations as shown in the attached table. Test 5 The same paint as in Test 4 was prepared, and the coated board was heated at 80°C for 30 minutes.
Let dry for a minute. The dry coating film with a thickness of 26 μm is MEK
It did not change even after being rubbed 100 times with a back and forth motion using the NFT 30016, and the Persause hardness was 24 when measured using NFT 30016.
The specular gloss at 60° measured according to ASTM standard D523-85 was 79%. Critical surface tension was 40 mN/m. The results of the stain resistance test and its persistence test show that there are limitations as shown in the attached table. Test 6 The same test piece as in Test 4 was prepared. the fluorinated composition, 4
0 g of commercially available hydroxylated polyfluorinated copolymer (50% butyl acetate solution, viscosity 2600
mPa/s, 1.3% hydroxyl group content), 6 g of hexamethylene diisocyanate trimmer, 352.5
g of methoxypropanol acetate and 0.05 g
It was prepared by mixing DBTL with a 10% butyl acetate solution. This fluorinated composition was applied to the coating of Test 4 for 30 minutes.
It was applied using a μm spiral applicator and left to dry at room temperature for 48 hours to obtain a coating film with a thickness of 4±1 μm. The critical surface tension was 21 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Test 7 The same specimens as Test 6 were prepared, but the solution of the fluorinated composition was dried in an oven at 80° C. for 30 minutes to a thickness of 4±μ.
A coating film of m was obtained. The critical surface tension was 20.7 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Example 3 In a 3.3 liter autoclave equipped with an effective stirring device, after vacuum degassing, 2 liters of tert-butanol and 30 g of 3-allyloxy-1,2-
Propanediol and 30g of the following formula [Chemical formula 16]: [
A fluorinated monomer represented by the following formula is introduced. The temperature of the autoclave was set to 70℃, and at this temperature 215g of C2
After adding H2 F2 and 84 g of C2 F4,
Add 5g of tertiary butyl perpivalate. The pressure is 20 bar. As the pressure decreases due to the copolymerization reaction, C2 H2
A mixture of F2 and C2 F4 in a molar ratio of 65/35 is added to compensate the pressure. For every 46 g of the above monomer mixture added, 5.5 g of 3-allyloxy-1,2-
Propanediol and 5.5 g of the following formula [Chemical formula 17]
: [0045] A compound represented by the following formula is added. After polymerizing for 3 hours, 8
g of tertiary butyl perpivalate is introduced to increase the rate of copolymerization. After 5 hours, a total of 44 g of 3-allyloxy-1,2-propanediol, 414 g of a monomer represented by the following formula [Chemical formula 18]: [Chemical formula 18], and 414 g of a molar ratio of 65/35
C2H2 F2 /C2 F4 monomer mixture. The autoclave was cooled, the residual monomer was degassed, and the contents of the autoclave were distilled under reduced pressure to 485 g.
The copolymer is recovered and dissolved in butyl acetate. The dry extract of the copolymer solution after washing with water is 68.9
%. The hydroxyl groups of the copolymer are chemically quantified in pyridine/phthalic anhydride solvent. As a result of the measurement, OH was 1.
It was 5 m equivalent/g. As a result of NMR analysis of fluorine 19, it was confirmed that the molar composition of the copolymer was as follows: [Chemical formula 19]: [Chemical formula 19] The intrinsic viscosity of this copolymer at a concentration of 1 g/dl in dimethylformamide solution at 25°C was 0.18 dl/g. Test 8 200 g of the above copolymer solution are mixed with 23.9 g of isophorone diisocyanate and 23.9 g of a 10% butyl acetate solution of DBTL. The viscosity is adjusted using 27 g of methoxypropanol acetate. Apply the obtained varnish to a thickness of 0 using a 100 μm spiral applicator.
．． Apply to a 7mm deoiled chromed aluminum plate. The specimens are left to dry at room temperature for 48 hours to obtain a dry coating with a thickness of 27 μm. This coating film does not change even if rubbed 100 times with MEK back and forth motion, and it does not change with NFT3001.
6 shows a Persauz hardness of 240s when measured according to
Specular gloss at 60 degrees measured according to ASTM standard D523-85 was 53%. Critical surface tension is 31mN
/m. The stain resistance is shown in the attached table. Test 9 200 g of the above copolymer are mixed with 40 g of a 90% isobutanol solution of etherified melamine formaldehyde resin and 0.25 g of p-toluenesulfonic acid. The viscosity is prepared using 40 g of propylene glycol diacetate. The obtained varnish is applied to a deoiled galvanized aluminum plate with a thickness of 0.8 mm using a 100 μm spiral applicator. The specimens are dried in an oven at 150° C. for 30 minutes to obtain a dry coating film with a thickness of 22 μm. This coating did not change after 100 rubbings with MEK in a back and forth motion and had a 60
The specular gloss at 30°C was 60%, and the persauz hardness was 225s when measured according to NFT30016. The critical surface tension was 31 mN/m. The stain resistance is shown in the attached table. Test 10 A base is prepared by dispersing 126 g of titanium dioxide, 160 g of the above copolymer solution, 28.8 g of butyl acetate, and 18 g of methoxypropanol acetate at 1500 rpm for 30 minutes. This white base 1
06.4 g, 20 g of the above copolymer solution, 21 g of hexamethylene diisocyanate trimmer, and 0.7
g of DBTL in 10% butylacetate solution and 5.2
g of methoxypropanol acetate. The obtained paint was applied to a thickness of 100 μm using a spiral applicator.
Apply to a 0.7 mm deoiled chromium-treated aluminum plate. The specimens are left to dry at room temperature for 48 hours to obtain a dry coating with a thickness of 26 μm. This coating film did not change even when rubbed 100 times with MEK back and forth motion, and the NFT
Persaud hardness 205s when measured according to 30016
The specular gloss at 60° measured according to ASTM standard D523-85 was 58%. The critical surface tension was 32.5 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Test 11 The same paint as in Test 10 was prepared and dried in an oven at 80° C. for 30 minutes. The resulting dry coating film with a thickness of 26 μm did not change even after being rubbed 100 times with MEK in a back and forth motion, and the specular gloss at 60° measured according to ASTM standard D523-85 was 69%. NFT30016
The Persauz hardness measured according to the method was 215s. The critical surface tension was 32.5 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Example 4 In a 3.3 liter autoclave equipped with an effective stirring device, after vacuum degassing, 2 liters of tert-butanol and 30 g of 3-allyloxy-1,2-propanediol were added. 30g formula: C8 F17C2 H
A fluorinated monomer represented by 4 -O-CH2 -CH=CH2 is introduced. Autoclave temperature to 70
℃ and at this temperature 215 g of C2 H2 F2 and 84 g of C2 F4 are added followed by 5 g of tertiary butyl perpivalate. The pressure is 20 bar. As the pressure decreases due to the copolymerization reaction, C2H
A mixture of 2 F2 and C2 F4 in a molar ratio of 65/35 is added to compensate the pressure. For every 46 g of this monomer mixture added, 5.5 g of 3-allyloxy-1,2-
Propanediol and 5.5g formula: C8 F17C
A compound represented by 2 H4 -O-CH2 -CH=CH2 is added. After 3 hours of polymerization, 8 g of tertiary butyl perpivalate are introduced to increase the rate of copolymerization. After 5 hours and 30 minutes, a total of 44 g of 3-allyloxy-1,2-propanediol and 44 g of formula: C8
F17C2 H4 -O-CH2 -CH=CH2
The molar ratio of the monomer represented by and 414g is 65/3
5 of the C2 H2 F2 /C2 F4 monomer mixture. The autoclave is cooled, residual monomer is degassed, and the contents of the autoclave are distilled under reduced pressure.4
56 g of copolymer is recovered. When this is dissolved in butyl acetate and washed with water, a copolymer solution with a dry extract of 52% is obtained. From the results of chemical determination of the hydroxy groups of this copolymer in the pyridine/phthalic anhydride solvent as described above, OH is 1.
It was 70 m equivalent/g. As a result of NMR analysis of fluorine 19, it was confirmed that the molar composition of this copolymer was the following formula [Chemical formula 20]. Concentration 1 in dimethylformamide solution at 25°C
The inherent viscosity of this copolymer in g/dl is 0.18 dl
/g. Test 12 100 g of the above copolymer solution was mixed with 17.4 g of hexamethylene diisocyanate trimmer and 2.2 g of DB.
Mix with 10% butyl acetate solution of TL. The viscosity is adjusted using 5.2 g of methoxypropanol acetate. The resulting varnish is applied to a deoiled, chromium-treated aluminum plate with a thickness of 0.7 mm using a 100 μm spiral applicator. The specimens are left to dry at room temperature for 48 hours to obtain a dry coating with a thickness of 21 μm. This coating did not change even after 100 times of back and forth rubbing with MEK, had a Persauz hardness of 212s when measured according to NFT30-016, and had a specular gloss of 60 degrees at 60 degrees when measured according to ASTM standard D523-85. %Met. The critical surface tension was 31.5 mN/m. The results of the stain resistance test are shown in the attached table. Test 13 A base is prepared by dispersing 97.2 g of titanium dioxide, 194.4 g of the above copolymer solution, and 20 g of methoxypropanol acetate at 1500 rpm for 30 minutes. To 233.7 g of this white base, 4.2 g of the above copolymer solution, 26.1 g of hexamethylene diisocyanate trimmer, and 0.8 g of DBTL 10
% butylacetate solution and 12 g of butylacetate. The resulting paint is applied to a 0.7 mm thick deoiled chromium-treated aluminum plate using a 100 μm spiral applicator. Place the test piece in an oven at 80℃ for 30 minutes.
Let dry for a minute. The obtained dry coating film with a thickness of 21 μm was ME
There was no change even after rubbing 100 times with a back and forth motion using K, and the Persauz hardness was measured according to NFT30016.
225s, and the specular gloss at 60 degrees measured according to ASTM standard D523-85 was 55%. The critical surface tension was 32.5 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Example 5 In a 3.3 liter autoclave equipped with an effective stirring device, after degassing under reduced pressure, 2 liters of tert-butanol and 22 g of triethylolpropane monoallyl ether of the formula [Chemical Formula 21]: [Chemical Formula 21] 30 g of a fluorinated monomer represented by the following formula are introduced. The temperature of the autoclave is 70℃, and at this temperature 215
g of C2 H2 F2 and 84 g of C2 F4 are added followed by the addition of 5 g of tert-butyl perpivalate. The pressure is 20 bar. As the pressure decreases due to the copolymerization reaction, C2 H2 F2 and C2 F4
The pressure is compensated by adding a 65/35 molar mixture of For every 46 g of this monomer mixture added, 8 g of trimethylolpropane monoallyl ether and 7.5 g of a compound represented by the following formula [Chemical formula 22]: [Chemical formula 22] are added. After polymerizing for 3 hours, 1
2 g of tertiary butyl perpivalate are introduced to increase the rate of copolymerization. After 6 hours, a total of 40 g of trimethylolpropane monoallyl ether, 37.5 g of a monomer represented by the following formula [Chemical formula 23]: [Chemical formula 23], and 368 g of a molar ratio of 65/3
5, a C2 H2 F2 /C2 F4 monomer mixture. The autoclave is cooled, residual monomer is degassed, and the contents of the autoclave are vacuum distilled to recover 371 g of copolymer. After dissolving this in butyl acetate and washing with water, a copolymer solution with a dry extractable content of 60% is obtained. As a result of chemically quantifying the hydroxyl groups of the copolymer in the above-mentioned pyridine/phthalic anhydride solvent, OH was
It was 1.36 m equivalent/g. As a result of NMR analysis of fluorine 19, the molar composition of this copolymer is shown in the following formula [Chemical formula 24]
: [0060] It was confirmed that it is represented by the following formula. The intrinsic viscosity of this copolymer at a concentration of 1 g/dl in dimethylformamide solution at 25° C. was 0.18 dl/g. Test 14 120 g of the above copolymer solution were dissolved in isobutanol at 9%
Mix 20 g of etherified melamine formaldehyde resin adjusted to 0%, 10 g of xylene, and 0.3 g of para-toluenesulfonic acid. 100% of the resulting varnish
It is applied using a μm spiral applicator to a deoiled, chromium-treated aluminum plate with a thickness of 0.7 mm. This test piece was dried in an oven at 145°C for 30 minutes to a thickness of 22
A dry coating of μm is obtained. This coating film did not change even after being rubbed 100 times with methyl ethyl ketone in a back and forth motion, and the Persauz hardness was measured according to NFT 30016.
225s, and the specular gloss at 60° measured according to ASTM standard D523-85 was 65%. The critical surface tension was 31.5 mN/m. The stain resistance results are shown in the attached table. Test 15 A base is prepared by dispersing 106.4 g of titanium dioxide, 177.4 g of the above copolymer solution, and 16 g of methoxypropanol acetate at 1500 rpm for 30 minutes. This white base 149.9g, 11.3g
of the above copolymer solution, 16 g of hexamethylene diisocyanate trimer, and 2.0 g of 10% of DBTL.
Add butyl acetate solution and 6 g of butyl acetate. The resulting paint is applied to a deoiled, chromium-treated aluminum plate with a thickness of 0.7 mm using a 100 μm spiral applicator. The specimens are left to dry at room temperature for 48 hours to obtain a dry coating with a thickness of 23 μm. This coating film did not change even if rubbed 100 times using MEK in a back and forth motion, and the N
Persaud hardness 22 when measured according to FT 30016
The specular gloss at 60° measured according to ASTM standard D523-85 was 63%. The critical surface tension was 32.5 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Example 6 In a 3.3 liter autoclave equipped with an effective stirring device, after degassing under reduced pressure, 2 liters of tert-butanol and 50 g of 3-allyloxy-1,2-
Propanediol and 40g formula: C8 F17C2
A fluorinated monomer of the form H4-O-CH2-CH=CH2 and 90 g of butyl vinyl ether are introduced. The temperature of the autoclave was set to 70°C, and at this temperature, 280 g of C2F3Cl and 240 g of C2
Add F4 and 10 g of tert-butyl perpivalate. The pressure is 15 bar. The copolymerization reaction is confirmed by a decrease in pressure. C2 F3Cl and C2 F4
The pressure is compensated by adding a 50/50 molar mixture of . For every 27 g of this monomer mixture added, 4.5 g of 3-allyloxy-1,2-propanediol and 4 g
C8 F17C2 H4 -O-CH2 CH=CH
2 and 6.8 g of butyl vinyl ether. After 5 hours, a total of 58.5 g of 3-allyloxy-1,
2-propanediol and 52 g of C8 F17C2
H4 -O-CH2 -CH=CH2 and 360g
The molar ratio of C2F3Cl/C2F4 is 50/50
and 88 g of butyl vinyl ether are introduced. The autoclave is cooled, residual monomer is degassed, and the contents of the autoclave are vacuum distilled to recover 700 g of copolymer. After dissolving this in ethyl acetate and washing with water, the dry extractable content of the copolymer solution was 65
%. As a result of chemically quantifying the hydroxyl groups of this copolymer in a pyridine/phthalic anhydride solvent using the method described above, it was found that O
H was 1.05 m equivalent/g. Fluorine 19 N
As a result of MR analysis, the molar composition of this copolymer was determined by the following formula [
It was confirmed that it is represented by [Chemical formula 25]. Concentration 1 g/d in dimethylformamide solution at 25°C
The intrinsic viscosity of this copolymer was 0.98 dl/g. Test 16 100 g of the above copolymer solution was mixed with 8.0 g of isoporone diisocyanate and 2.3 g of 10% DBTL.
Mix with butyl acetate solution. Viscosity is 15.2g
of methoxypropanol acetate. The obtained varnish is applied to a deoiled, chromium-treated aluminum plate with a thickness of 0.7 mm using a 100 μm spiral applicator. The specimens are left to dry at room temperature for 48 hours to obtain a dry coating with a thickness of 26 μm. This coating showed no change even after being rubbed 100 times with MEK in a back and forth motion, had a Persause hardness of 230s when measured according to NFT 30016, and complied with ASTM standard D523-
The specular gloss at 60° measured according to No. 85 was 68%. The critical surface tension was 31.5 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Test 17 110 g of titanium dioxide, 160 g of the above copolymer solution, and 30 g of butyl acetate were heated at 1500 rpm.
Prepare the base by dispersing at m for 30 minutes. To 150 g of this white base, 20 g of the above copolymer solution and 13.4 g of the above copolymer solution were added.
g of hexamethylene diisocyanate trimmer, and 0
．． 5 g of DBTL in 10% butylacetate solution and 12
g of butyl acetate. 1 of the obtained paint
The sample is applied using a 00 μm spiral applicator to a 0.7 mm thick deoiled, chromium-treated aluminum plate. A dried coating film with a thickness of 26 μm obtained by drying the test piece at room temperature for 48 hours did not change even when rubbed 100 times by back and forth motion using MEK, and exhibited a Persause hardness of 240 s when measured according to NFT 30016. ASTM standard D523-8
The specular gloss at 60° measured according to No. 5 was 60%. The critical surface tension was 32 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. Test 18 The same paint as in test 12 is prepared, in this case the coated sheet is dried in an oven at 80° C. for 30 minutes. The resulting dry coating film with a thickness of 26 μm did not change even when rubbed 100 times with MEK in a back and forth motion, and the NFT 30016
It showed a Persauz hardness of 245s when measured according to the AS
The specular gloss at 60° measured according to TM standard D523-85 was 65%. Example 7 In a 3.3 liter autoclave equipped with an effective stirring device, after vacuum degassing, 2 liters of tertiary butanol, 50 g of trimethylolpropane monoallyl ether and 40 g of Formula [Chemical formula 26]: [0
A fluorinated monomer of the following formula and 75 g of butyl vinyl ether are introduced. Autoclave temperature to 70℃
At this temperature, 280g of C2F3Cl and 2
Add 40 g C2F4 and 10 g tert-butyl perpivalate. The pressure is 15 bar. The copolymerization reaction is confirmed by a decrease in pressure. C2 F
The pressure is compensated by adding a 50/50 molar mixture of 3Cl and C2F4. 27g of the above monomer mixture
For each addition, 6 g of trimethylolpropane monoallyl ether and 5.4 g of the following formula: 00
70 Add the compound [Image Omitted] and 5.6 g of butyl vinyl ether. After 5 hours, a total of 78 g of trimethylolpropane monoallyl ether and 70 g of the following formula [Chemical formula 28]:
A compound of formula 28 and 360 g of C2F3Cl/C2F
4 in a molar ratio of 50/50 and 74 g of butyl vinyl ether. The autoclave is cooled, residual monomer is degassed, and the contents of the autoclave are vacuum distilled to recover 770 g of copolymer. After dissolving this in ethyl acetate and washing with water, the dry extractable content of the copolymer solution is 65%. As a result of chemically quantifying the hydroxyl groups of the copolymer in the above-mentioned pyridine/phthalic anhydride solvent, the OH content was 1.5 m equivalent/g. As a result of NMR analysis of fluorine 19, it was confirmed that the molar composition of this copolymer was represented by the following formula [Chemical formula 29]. Concentration 1 g/d in dimethylformamide solution at 25°C
The intrinsic viscosity of this copolymer in liters was 0.98 dl/g. Test 19 100 g of the above copolymer solution was mixed with 19.2 g of hexamethylene diisocyanate trimmer and 2.3 g of DB.
Mix with 10% butyl acetate solution of TL. The viscosity is adjusted using 10 g of methoxypropanol acetate. The resulting varnish is applied to a deoiled, chromium-treated aluminum plate with a thickness of 0.7 mm using a 100 μm spiral applicator. Place the test piece in an oven at 80°C.
Dry for 0 minutes to obtain a dry coating film with a thickness of 22 μm. This coating shows no change even after being rubbed 100 times with MEK in a back and forth motion. Further, the Persause hardness measured according to NFT 30016 was 207 s, and the specular gloss at 60° measured according to ASTM standard D523-85 was 62%. Critical surface tension was 30 mN/m. The stain resistance results are shown in the attached table. Test 20 A base is prepared by dispersing 117.8 g of titanium dioxide, 181.4 g of the above copolymer solution, and 20 g of methoxypropanol acetate at 1500 rpm for 30 minutes. To 59.6 g of this white base, 9.4 g of the above copolymer solution, 19.2 g of hexamethylene diisocyanate trimer, and 1.8 g of 10% DBTL were added.
Add butyl acetate solution and 5 g of butyl acetate. The resulting paint is applied to a deoiled, chromium-treated aluminum plate with a thickness of 0.7 mm using a 100 μm spiral applicator. The test piece is dried in an oven at 80° C. for 30 minutes to obtain a dry coating film with a thickness of 22 μm. This coating is
It remained unchanged even after being rubbed 100 times with MEK in a back and forth motion, had a Persaise hardness of 217s when measured according to NFT 30016, and had a specular gloss of 59% at 60° when measured according to ASTM standard D523-85. Ta. The critical surface tension was 30.5 mN/m. The results of the stain resistance test and its persistence test are shown in the attached table. [Table 1] [Table 2] [Table 2] [Table 3] [Table 3] [Table 4] [Table 5] [0079] Preferred specific examples of the present invention have been described above. However, it is clear that the present invention is not limited to these examples, but includes the scope defined in the claims, as well as improvements, changes, and equivalents thereof.

Claims (18)

[Claims] 1. A curable fluorinated copolymer comprising a copolymerized residue of a fluoride monomer and an allyl monomer, wherein (a) the copolymerized residue of the fluoride monomer comprises tetrafluoroethylene and chlorotrifluoroethylene; At least one fluoride monomer selected from ethylene and vinylidene fluoride, and (b) the copolymerized residue of the allyl monomer is as follows [Chemical 1]: [Chemical 1
] (Here, R1 is H or CH2OH, and R2
is OH or CH2OH and R3 is CH3
or OH, and R1 and R3 cannot be H and CH3 at the same time), and furthermore, (c
) Following [Chemical 2]: [Chemical 2] (where n is 3 to 12, and R4 is H or CH
3, and X is CH2-O or the following [Chemical 3]: [Chemical 3] Curable fluorinated copolymer. 2. Per 100 moles of all copolymerized monomers, (a) 14 to 4 tetrafluoroethylene;
5 mol, (b) 25 to 81 mol of chlorotrifluoroethylene, vinylidene fluoride or mixtures thereof, (
c) 4 to 15 moles of allyl polyol, (d) 1 to 1 of fluorinated allyl monomers or fluorinated acrylic monomers
A copolymer according to claim 1 having a composition of 7 molar. 3. A non-hydroxylated vinyl ether residue represented by the formula CH2 = CH-O-R5 (wherein R5 is a linear or side-chain alkyl group having 2 to 13 carbon atoms) The copolymer according to claim 1 or 2, comprising a group. 4. The copolymer according to claim 1, wherein the non-hydroxylated vinyl ether is added in an amount of 33 moles or less per 100 moles of total monomers required for the formulation. [Claim 5] Any one of claims 1 to 4, wherein the ratio of the number of moles of vinylidene fluoride to the total number of moles of tetrafluoroethylene and chlorotrifluoroethylene is represented by the following [Formula 1]: [Formula 1] Copolymer according to item 1. 6. Claims 1 to 4 containing 20 moles or less of C2 H2 F2, wherein the molar ratio of C2 F4 to C2 F3Cl in the composition is represented by the following [Formula 2]: [Formula 2] The copolymer according to any one of . 7. Intrinsic viscosity at 1 g/dl concentration in dimethylformamide solution at 25°C is 0.06 to 1 dl/
The copolymer according to any one of claims 1 to 6, which is g. 8. The copolymer according to any one of 1 to 7, which is a solution in an organic solvent. 9. The copolymer according to claim 8, wherein the solvent is alcohol or acetate. 10. A method for producing a curable copolymer based on a fluorinated monomer and an allyl monomer, comprising: (a) tetrafluoroethylene (b) chlorotrifluoroethylene, vinylidene fluoride or a mixture thereof ( c) The following [Chemical formula 4]: [Chemical formula 4] (Here, R1 represents H or CH2OH, and R2
represents OH or CH2 OH, R3 is CH3
or OH, and R1 and R3 cannot be H and CH3 at the same time) Allyl polyol (d) represented by the following formula [Chemical formula 5]: [Chemical formula 5] (where n is 3 to 12 and , R4 is H or CH
3, and X is CH2-O or the following [Chemical formula 6]: [Chemical formula 6] Method. 11. Per 100 moles of the monomer to be copolymerized, (a) 14 to 45 tetrafluoroethylene;
moles, (b) 25 to 81 moles of chlorotrifluoroethylene, vinylidene fluoride or mixtures thereof, (c
) 4 to 15 allyl monomers in the form of allyl polyols
11. The process according to claim 10, wherein (d) 1 to 7 moles of allyl or acrylic monomer having a fluorocarbon chain are used. 12. Claim 1, in which a vinyl ether as defined in claim 3 is added in addition to the monomers necessary for the copolymer reaction.
0 or 11. 13. The process according to claim 12, wherein up to 33 moles of vinyl ether are added per 100 moles of monomer to be copolymerized. 14. The method according to claim 10, wherein the copolymerization is carried out by solution polymerization in an organic solvent. 15. The method according to claim 14, wherein the organic solvent is alcohol or acetate. 16. The method according to claim 10, wherein the copolymerization temperature is 30 to 120°C. 17. Process according to claim 10, wherein the copolymerization pressure is between 10 and 80 bar. 18. A stain- and stain-resistant paint or varnish dissolved in an organic solvent comprising a curable fluorinated copolymer according to any one of claims 1 to 7.